The present invention relates to the non-cryogenic separation of gas mixtures. The invention provides a composition of matter comprising a polymeric membrane which exhibits superior properties when used for the non-cryogenic separation of gases such as air.
It has been known to use a polymeric membrane to separate air into components. Various polymers have the property that they allow different gases to flow through, or permeate, the membrane, at different rates. A polymer used in air separation, for example, will pass oxygen and nitrogen at different rates. The gas that preferentially flows through the membrane wall is called the “permeate” gas, and the gas that tends not to flow through the membrane is called the “non-permeate” or “retentate” gas. The selectivity of the membrane is a measure of the degree to which the membrane allows one component, but not the other, to pass through.
A membrane-based gas separation system has the inherent advantage that the system does not require the transportation, storage, and handling of cryogenic liquids. Also, a membrane system requires relatively little energy. The membrane itself has no moving parts; the only moving part in the overall membrane system is usually the compressor which provides the gas to be fed to the membrane.
A gas separation membrane unit is typically provided in the form of a module containing a large number of small, hollow fibers made of the selected polymeric membrane material. The module is generally cylindrical, and terminates in a pair of tubesheets which anchor the hollow fibers. The tubesheets are impervious to gas. The fibers are mounted so as to extend through the tubesheets, so that gas flowing through the interior of the fibers (known in the art as the bore side) can effectively bypass the tubesheets. But gas flowing in the region external to the fibers (known as the shell side) cannot pass through the tubesheets.
In operation, a gas is introduced into a membrane module, the gas being directed to flow through the bore side of the fibers. One component of the gas permeates through the fiber walls, and emerges on the shell side of the fibers, while the other, non-permeate, component tends to flow straight through the bores of the fibers. The non-permeate component comprises a product stream that emerges from the bore sides of the fibers at the outlet end of the module.
Alternatively, the gas can be introduced from the shell side of the module. In this case, the permeate is withdrawn from the bore side, and the non-permeate is taken from the shell side.
An example of a membrane-based air separation system is given in U.S. Pat. No. 4,881,953, the disclosure of which is incorporated by reference herein.
Other examples of fiber membrane modules are given in U.S. Pat. Nos. 7,497,894, 7,517,388, 7,578,871, and 7,662,333, the disclosures of which are all hereby incorporated by reference.
The effectiveness of a membrane in gas separation depends not only on the inherent selectivity of the membrane, but also on its capability of handling a sufficiently large product flow. A membrane module is therefore evaluated according to flux, i.e. the flow rates of various components through the membrane, as well as according to selectivity.
A polymeric fiber for use in the module described above is made from a mixture known as a “spin dope”. The spin dope includes a polymeric material or precursor, a solvent which dissolves the polymer, and a non-solvent in which the polymer is insoluble. The spin dope comprises the material which is spun into a fiber. In general, one tailors the spin dope to control the formation of the fiber. That is, the composition of the spin dope determines when the polymeric material will undergo a transformation from a state in which it is intermixed and homogeneous in the spin dope, to a state in which the polymer is the principal component.
The fiber formulation is defined by three parameters, namely 1) the percentage of polymer in the spin dope, 2) the type of polymer solvent(s), and 3) the non-solvent in the mixture. The terms “solvent” and “non-solvent” are used to mean, respectively, the components of the spin dope in which the polymer is soluble and insoluble.
The present invention provides a composition for use in making a gas-separation membrane in which both the gas flux and selectivity are improved. The polymeric membrane of the present composition therefore reduces the capital cost for gas-separation systems.